Pigmented actinic light polymerizable coating compositions containing phenanthrenequinone

ABSTRACT

Coatings of actinic light polymerizable coating compositions containing organic polymerizable material containing a plurality of sites of ethylenic unsaturation, phenanthrenequinone and ultraviolet light absorbing pigment are polymerized by exposing them to actinic light of a wavelength where absorption by the pigment is insubstantial.

The use of actinic light polymerizable coating compositions is becomingmore widespread. This growing interest is primarily occasioned by thelow power requirements of actinic light sources as compared to thermalovens, by the low levels of environmental pollution which can beobtained, and by the minimal space required for actinic light curingequipment. Nonetheless, several problems have arisen which have retardedthe use of actinic light polymerizable coating compositions in certainareas.

One problem is that of achieving adequate hiding in coating systemswhere hiding of the substrate is desired. In theory, one method ofobtaining hiding is to incorporate pigments into the coatingcomposition. Unfortunately, many of the pigments known to provideopacity to nonradiation polymerizable coatings absorb strongly in mostareas of the ultraviolet light region, viz., electromagnetic radiationhaving wavelengths in the range of from about 180 nanometers to about400 nanometers. This absorption prevents adequate quantities ofultraviolet light from penetrating very far into the interior of thefilm. The result is inadequate polymerization of the interior region ofthe coating, or, using the terminology of the art, inadequate "throughcure". Ultraviolet light absorbing hiding pigments which are desirablyused in coating compositions due to their excellent hidingcharacteristics include, but are not limited to, titanium dioxide(including rutile and anatase), antimony trioxide, zinc oxide, zirconiumoxide, zinc sulfide, lithopone and mixture thereof. The preferredpigment is titanium dioxide. Rutile is especially preferred.

It has now been found that the use of 9, 10-phenanthrenquinone inactinic light polymerizable coating compositions containing ultravioletlight absorbing hiding pigments allows the interior of coating of thecomposition to be adequately polymerized. Although it is not desired tobe bound by any theory, it is believed that the reasonphenanthrenequinone performs satisfactorily is as follows: Although thepigments absorb light strongly in the ultraviolet region at a wavelengthof about 200 namometers, the absorption diminishes as the wavelength oflight is increased. At about 400 nanometers, the absorption hasdiminished to a small value so that a significant portion of the lightis able to reach the interior of the coating. The absorption ofphenanthrenequinone, however, remains at a high value well into thevisible spectrum before it too diminishes to a small value.Phenanthrenequinone is, therefore, suitable for pigmented systemsbecause it absorbs actinic light having a wavelength in a region ofsubstantial pigment transparency and uses the energy of the absorbedphotons to produce free radicals capable of causing polymerization oforganic polymerizable material containing a plurality of sites ofethylenic unsaturation.

According to the present invention, a substrate is coated with a coatingcomposition containing (1) organic polymerizable material containing aplurality of sites of ethylenic unsaturation and capable of being freeradically addition polymerized by interaction with phenanthrenequinoneupon exposure to actinic light, (2) phenanthrenequinone, and (3)ultraviolet light absorbing hiding pigment. The coated substrate is thenexposed to actinic light which has a wavelength such that theultraviolet light absorbing hiding pigment is substantially transparentthereto and which is absorbable by the phenanthrenequinone to producefree radicals capable of causing polymerization of the organicpolymerizable material to thereby polymerize the coating into a hard,infusible film.

There are many types of organic polymerizable materials which may beused in the practice of the invention. In general, these moleculescontain a plurality of sites of ethylenic unsaturation and are capableof being free radically addition polymerized by interaction with thearomatic ketone photopolymerization activator and phenanthrenequinoneupon exposure to actinic light. The sites of ethylenic unsaturation maylie along the backbone of the molecule or they may be present in sidechains attached to the molecular backbone. As a further alternative,both of these arrangements may be present concurrently. Most often, theorganic polymerizable material comprises ethylenically unsaturatedpolyester containing a plurality of sites of ethylenic unsaturation,polymer having a plurality of sites of acrylic unsaturation, monomerhaving a plurality of sites of acrylic unsaturation or mixture thereof.

The ethylenically unsaturated polyesters constitute a useful class oforganic polymerizable material. These polyesters are ordinarilyesterification products of ethylenically unsaturated polycarboxylicacids and polyhydric alcohols. Usually, the ethylenic unsaturation is inthe alpha, beta position.

The ethylenically unsaturated polycarboxylic acids includes maleic acid,fumaric acid, aconitric acid, itaconic acid, citraconic acid, mesaconicacid, muconic acid and dihydromuconic acid and halo and alkylderivatives of such acids. The preferred acids are maleic acid andfumaric acid. Especially preferred is maleic acid. Mixtures ofethylenically unsaturated polycarboxylic acids may be used or only asingle such acid may be employed. The anhydrides of these acids, wherethe anhydrides exist, are, of course, embraced by the term "acid", sincethe polyesters obtained therefrom are essentially the same whether theacid or anhydride is used in the reaction.

One or more saturated polycarboxylic acids may optionally be utilized incombination with the ethylenically unsaturated acid or anhydride in thepreparation of unsaturated polyesters. Such acids, especially thesaturated dicarboxylic acids, increase the length of the polyesterwithout adding additional crosslinking sites, which is a desired featurein some polyesters. Saturated tricarboxylic acids and saturated acids ofhigher carboxylic functionality may be used to provide branching wherethis is desirable.

For purposes of the present invention, the aromatic nuclei of aromaticacids such a phthalic acid are generally regarded as saturated since thedouble bonds do not ordinarily react by addition as do ethylenic groups.Therefore, wherever the term "saturated" is utilized, it is to beunderstood that such term includes aromatic unsaturation or other formof unsaturation which does not react by addition, unless otherwisequalified.

Examples of useful saturated polycarboxylic acids include oxalic acid,malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinicacid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid.2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid,3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, adipic acid,pimelic acid, suberic acid, azelaic acid, sebaccic acid, phthalic acid,isophthalic acid, terephthalic acid, tetrachlorophthalic acid,1,2-hexahydrophthalic acid, 1,3-hexahydrophthalic acid,1,4-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid andtrans-1,4-cyclohexanedicarboxylic acid. As in the case of theethylenically unsaturated polycarboxylic acids, the anhydrides of thesaturated acids, where anhydrides exist, are embraced by the term "acid"since the polyesters obtained therefrom are essentially the same.

The ethylenically unsaturated polycarboxylic acids are usually presentin an amount in the range of from about 10 mole percent to about 100mole percent of the polycarboxylic acids employed. Preferably, they arepresent in the range of from about 50 mole percent to about 100 molepercent.

The polyhydric alcohols useful in preparing ethylenically unsaturatedpolyesters include saturated polyhydric alcohols such as ethyleneglycol, 1,3-propanediol, propylene glycol, 2,3-butanediol1,4-butanediol, 2-ethylbutane-1,4-diol, 1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,2,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane,2,2-diethylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol,3-methylpentane-1,4-diol, 2,2-diethylbutane-1,3-diol, 4,5-nonanediol,diethylene glycol, triethylene glycol, dipropylene glycol, glycerol,pentaerythritol, erythritol, sorbitol, mannitol,1,1,1-trimethylolpropane, trimethylolethane, and2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate.Ethylenically unsaturated polyhydric alcohols such as 2-butene-1, 4-diolmay be used alone or in admixture with the saturated polyhydricalcohols. Of course, mixtures of saturated polyhydric alcohols ormixtures of unsaturated polyhydric alcohols may be employed. Ifunsaturated polyhydric alcohols are used to introduce ethyleneunsaturation into the polyester, the preparation of ethylenicallyunsaturated polycarboxylic acid may be reduced correspondingly, ifdesired.

A mixture of ethylenically unsaturated polyesters containing a pluralityof sites of ethylenic unsaturation may be used, if desired.

Another useful class of organic polymerizable material is polymer havinga plurality of sites of acrylic unsaturation. The sites of acrylicunsaturation may be provided by acrylyl groups or α-substituted acrylylgroups such as methacrylyl, ethacrylyl and α-chloroacrylyl. The sites ofacrylic unsaturation may be terminal groups of the polymer, they may bein sidechains attached to the molecular backbone of the polymer or both.

Polymers having acrylic unsaturation in sidechains attached to themolecular backbone are usually prepared by including one or moremonomers which, when interpolymerized with other monomers, to form thepolymer, provides reactive sites attached to the polymer along thebackbone. Acrylically unsaturated compounds having at least onefunctional group which will react with the reactive sites on thepolymeric backbone are then used to introduce the acrylic unsaturationinto the molecule. The usual reactive sites attached directly orindirectly to the polymer are hydroxy, amino, carboxy, carbamyl,isocyanato or epoxy. Hydroxy or carboxy are most often used. When thereactive sites are hyroxy, the acrylically unsaturated compound usuallyhas carboxy, haloformyl (most often chloroformyl) or isocyanatofunctionality. When the reactive sites on the polymer are amino, theacrylically unsaturated compound usually has isocyanato, haloformyl(again, most often chloroformyl) or epoxy functionality. When thereactive sites on the polymer are carboxy, the acrylically unsaturatedcompound generally has hydroxy, epoxy or isocyanato functionality. Whenthe reactive sites are carbamyl, they are usually reacted withformaldehyde to produce N-methylol carbamyl groups. When the reactivesites are isocyanato, the acrylically unsaturated compound ordinarilycontains hydroxy or carboxy functionality. When the reactive sites areepoxy (usually glycidyl), the acrylically unsaturated compound generallyhas carboxy functionality. The acrylically unsaturated compoundordinarily contains carboxy, haloformyl or isocyanato functionality.

The polymer having reactive sites attached thereto can itself be any ofmany types, as for example, polyacrylates, polyamides, polyesters,polyethers or polyurethanes.

The term polyacrylate is used in its broadest sense to include not onlypolymerized unsubstituted acrylates, but also polymerized α-substitutedacrylates, such as methacrylates, ethacrylates and α-chloroacrylates.Compounds from any of these subclasses may be used alone, but mostoften, compounds from two or more subclasses are interpolymerized.

Examples of suitable monomers which may be used in the preparation ofthe polyacrylate polymer include methyl acrylate, ethyl acrylate, propylacrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate,sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate,heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate,dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propylmethacrylate, isopropyl methacrylate, butyl methacrylate, isobutylmethacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amylmethacrylate, hexyl methacrylate, heptyl methacrylate, octylmethacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecylmethacrylate methyl α-chloroacrylate, ethyl α-chloroacrylate, propylα-chloroacrylate, hexyl α-chloroacrylate, octyl α-chloroacrylate, decylα-chloroacrylate and dodecyl α-chloroacrylate. Esters of unsubstitutedacrylic acid and methacrylic acid are most often used.

Acrylic monomers which introduce reactive sites to the polymer moleculeinclude acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,3-hydroxypropyl acrylate, glycidyl acrylate, acrylamide, 2-aminoethylacrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropylmethacrylate, 3-hydroxypropyl methacrylate, glycidyl methacrylate,methacrylamide, 2-aminoethyl methacrylate, 3-aminopropyl methacrylateand α-chloracrylic acid.

Other ethylenically unsaturated monomers are often included. Examples ofthese compounds are styrene and α-methylstyrene.

The amount of acrylic monomers which are used to introduce reactivesites to the polymer molecule may vary widely, but they are ordinarilypresent in the range of from about 3 percent to about 50 percent byweight of the ethylenically unsaturated monomers interpolymerized. Anamount in the range of from about 4 percent to about 25 percent is mostoften the case.

Addition polymerization may be effectuated by combining theethylenically unsaturated monomers with a free radical initiator andheating the mixture. Exemplary free radical initiators are organicperoxides such as ethyl peroxide and benzoyl peroxide; hydroperoxidessuch as methyl hydroperoxide, certain azo compounds such asα,α'-azobisisobutyronitrile and γ, γ'-azobis(γ-cyanovaleric acid);persulfates; peracetates such as methyl peracetate and tert-butylperacetate; peroxalates such as dimethyl peroxalate and di(tert-butyl)peroxalate; disulfides such as dimethyl thiuram disulfide and ketoneperoxides such as methyl ethyl ketone peroxide. The polymerization maybe accomplished in the presence or absence of an inert solvent.Temperatures in the range of from about 75° F. to about 400° F. aregenerally employed. More often, temperatures in the range of from about100° F. to about 300° F. are used.

When the polymer is a polyamide, polyester, polyether or polyurethane,the principles are analogous to those given for the polyacrylates. Theknown reactions for forming such polymers will, of course, be usedinstead of the addition polymerization reaction illustrated above forthe polyacrylates.

Other examples of satisfactory polymers having a plurality of sites ofacrylic unsaturation are acrylic polyester and acrylic polyamidemolecules represented by the formulae: ##STR1## wherein n is an integerin the range of from 1 to 4;

each R independently represents a divalent aliphatic,

cycloaliphatic or aromatic hydrocarbon radical having from 1 to 10carbon atoms;

each R' independently represents hydro, methyl or ethyl;

and each A independently represents 0 or NH.

It is preferred that every A represent 0. The polyester and polyamideoligomers represented by formula (I) may be prepared by reactingdicarboxylic acids or acid amides and dihydric alcohols or diamines andthen reacting the product with an unsubstituted acrylic acid or anα-substituted acrylic acid. The acrylic polyester and polyamideoligomers represented by formula (II) may be prepared by reacting ahydroxy functional monocarboxylic acid, a dimer, trimer or a tetramer ofsuch acid, an amino functional monocarboxylic acid or a dimer, trimer ortetramer of such acid with an unsubstituted or α-substituted acrylicacid. Where desired, the lactone may be used in lieu of the hydroxyfunctional monocarboxylic acid and the lactam may be used in place ofthe amino functional monocarboxylic acid.

A mixture of polymers having a plurality of sites of acrylicunsaturation may be used, if desired.

Another useful class of organic polymerizable material is monomer havinga plurality of sites of acrylic unsaturation. Such monomers generallycomprise divalent, trivalent or tetravalent organic radicals whose bondsare satisfied with unsubstituted acrylyloxy or α-substituted acrylyloxygroups. The polyvalent radical may be aliphatic, cycloaliphatic oraromatic. Usually, the molecular weight of the monomer is in the rangeof from about 170 to about 1000. Examples of such monomers are thediacrylates and dimethyacrylates of ethylene glycol, 1,3-propanediol,propylene glycol, 2,3-butanediol, 1,4-butanediol,2-ethylbutane-1,4-diol, 1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,2,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane,2,2-dimethylpropane-1,3-diol, 3-methylpentane-1,4-diol, 4,5-nonanediol,diethylene glycol, triethylene glcyol, propylene glycol,5,5-dimethyl-3,7-dioxanonane-1,9-diol, 2,2-dimethyl-3-hydroxypropyl2,2dimethyl-3-hydroxypropionate, Bisphenol A-diglycidyl ether,1,4-butanediol diglycidyl ether and neopentyl glycol diglycidyl ether;the triacrylates, trimethacrylates, diacrylates and dimethacrylates ofglycerol, 1,1,1-trimethylolpropane and trimethylolethane; and thetetracrylates, tetramethacrylates, triacrylates, trimethacrylates,diacrylates and dimethacrylates of pentaerythritol and erythritol. Theacrylic groups on the monomer molecules are usually the same, but theymay be different as exemplified by the compound2,2-dimethyl-1-acrylyloxy-3-methacrylyloxypropane.

A mixture of monomers having a plurality of sites of acrylicunsaturation may be used, if desired.

Additional monomers having one or more vinyl groups which crosslink withthe organic polymerizable material containing a plurality of sites ofethylenic unsaturation heretofore described may optionally be present inthe coating composition. Examples of N-vinyl-2-pyrrolidone, styrene,α-methylstyrene, divinyl benzene, vinyl toluene, vinyl benzoate, vinylacetate, vinyl proprionate and diallyl phthalate. Particularly preferredare monomers having monoacrylic functionality which crosslink with theresin having acrylic unsaturation which may optionally be present in thecoating composition. Examples of monoacrylic functional monomers whichmay be used are methyl acrylate, methyl methacrylate, ethyl acrylate,ethyl methacrylate, propyl acrylate, propyl, methacrylate, butylacrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, octylacrylate and octyl methacrylate. The preferred vinyl functional monomersare liquid compounds miscible with the resin. The use of one or morevinyl functional monomers is desirable. A benefit is that the vinylfunctional monomer usually acts as a reactive solvent for the resinthereby providing coating compositions having a satisfactorily lowviscosity without using an inordinate amount, if any at all, ofvolatile, nonreactive solvent.

The vinyl functional monomer, or mixtures of vinyl functional monomers,may be employed over a broad range. At the lower end of the range, novinyl functional monomer need be used. At the upper end of the range,about 80 percent by weight of the binder can be vinyl functionalmonomer. Often, the vinyl functional monomer will be present in thecoating composition in the range of from about 1 to about 80 percent byweight of the binder of the coating composition. Ordinarily, when used,the vinyl functional monomer will be in the range of from about 15 toabout 30 percent by weight of the binder.

Extender pigments which are generally transparent to ultraviolet lightare optional ingredients which are often included in the coatingcomposition. Examples of suitable extender pigments are finely dividedparticles of silica, barytes, calcium carbonate, talc, magnesiumsilicate, aluminum silicate, etc. When used, extender pigment isgenerally present in an amount in the range of from about 1 to about 70percent by weight of the coating composition. An amount in the range offrom about 1 to about 50 percent is more often employed. Most often, itis present in the range of from about 1 to about 35 percent by weight ofthe coating composition. Although a single extender pigment isordinarily used, mixtures of several extender pigments are satisfactory.

Another optional ingredient which is often included in the coatingcomposition is an inert volatile organic solvent. Mixtures of severalinert volatile organic solvents may be used when desired. Examples ofsuitable inert volatile organic solvents are acetone, methyl ethylketone, methyl isobutyl ketone, methyl alcohol, ethyl alcohol, propylalcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, isobutylalcohol, tert-butyl alcohol, amyl alcohol, hexyl alcohol, 2-ethylhexylalcohol, cellosolve, ethyl cellosolve, cellosolve acetate, 2-ethylhexylacetate, tetrahydrofuran, and aliphatic naphtha.. When inert volatileorganic solvent is used, it is usually present in the range of fromabout 1 to about 15 percent by weight of the vehicle.

Another optional ingredient is resinous pigment dispersant or grindingvehicle. There are many resinous dispersants which are commerciallyavailable for that purpose. These resins are often low molecular weightresins which have a high carboxyl content. Illustrative of such pigmentdispersants are the so-called acrysol dispersants such as Acrysol I-94,a copolymer of butyl acrylate, methyl methacrylate, styrene and acrylicacid, available commercially from the Rohm and Haas Company. Thesedispersants are used in the manner and in amounts known to the art.

Conventional plasticizers such as dibutyl phthalate, butyl benzylphthalate, diisooctyl phthalate, decyl butyl phthalate, diisooctyladipate, dibutyl sebacate, butyl benzoate triisooctyl trimellitate,n-octyl, n-decyl trimellitate, and tricresyl phosphates and flowpromoters such as phenyl benzoate, dibenzyl ketone, benzyl methyl ketoneand the like may also be optionally included in amounts customary in theart.

Various conventional chain modifying agents or chain-transfer agents maybe included in the mixture. The preferred chain-transfer agents are themercaptan compounds such as dodecyl mercaptan, tertiarydodecylmercaptan, octyl mercaptan, hexyl mercaptan and the like. The quantityand manner of use are also known in the art.

Any of the conventional viscosity control agents may be optionallyemployd in the composition. The preferred materials are resinous orpolymeric viscosity control agents. Many of these resinous materials areavailable. Illustrative of such materials are cellulose acetatebutyrate, sodium carboxymethyl cellulose and the like. The use of suchresinous or polymeric viscosity control agents is advantageous in thatit permits the mixture to be prepared in the form of a viscous mass orsyrup having sufficient viscosity to remain in place on the substrateuntil polymerization is effected. These viscosity control agents areused in the manner and in amounts known to the art.

The amount of organic polymerizable material having a plurality of sitesof ethylenic unsaturation present in the polymerizable coatingcomposition is subject to wide variation. The material is ordinarilypresent in an amount in the range of from about 20 to 100 percent byweight of the binder of the coating composition. An amount in the rangeof from about 50 to 100 percent is typical. From about 80 to 100 percentby weight of the binder is preferred.

The amount of phenanthrenequinone present in the polymerizable coatingcomposition may also be widely varied. Ordinarily, thephenanthrenequinone is present in an amount in the range of from about0.01 percent to about 10 percent by weight based on the weight of thebinder of the polymerizable coating composition. Most often, an amountin the range of from about 0.02 percent to about 7 percent is used. Fromabout 0.03 percent to about 5 percent by weight based on the weight ofthe binder is preferred.

The ultraviolet light absorbing hiding pigment should constitute atleast about 5 percent by weight of the actinic light polymerizablecoating composition. Amounts in the range of from about 5 percent toabout 70 percent by weight of the polymerizable coating composition aresatisfactory. From about 20 percent to about 70 percent is typical. Anamount in the range of from about 33 percent to about 50 percent byweight is preferred.

The coating compositions of the invention are usually prepared by simplyadmixing the various ingredients. Although mixing is usuallyaccomplished at room temperature, elevated temperatures are sometimesused. The maximum temperature which is usable depends upon the heatstability of the ingredients. Temperatures above about 200° C. are onlyrarely employed.

The actinic light polymerizable coating compositions of the inventionare generally used to form polymerized adherent coatings on substrates.The substrate is coated with the coating composition using substantiallyany technique known to the art. These include spraying, curtain coating,dipping roller application, printing, brushing, drawing and extrusion.The coating is polymerized by exposing the coated substrate to actiniclight which has a wavelength such that the ultraviolet light absorbinghiding pigment is substantially transparent thereto and which isabsorbable by the phenanthrenequinone to produce free radicals capableof causing polymerization of the organic polymerizable materialcontaining a plurality of sites of ethylenic unsaturation to therebypolymerize the coating into a hard, infusible film. Usually, the actiniclight has a wavelength in the range of from about 380 to about 500nanometers, although other wavelengths in keeping with the generalprinciples of the invention may be used in some cases. Sources whichemit only actinic light of one or more wavelengths in the range of fromabout 380 to about 500 nanometers and sources which emit actinic lightof such wavelength and light of wavelengths longer than 500 nanometersmay be used. However, it is preferred to use sources which emit both inthe ultraviolet light range, viz., wavelengths in the range of fromabout 185 to about 380 nanometers as well as actinic light having awavelength in the range of from about 380 to about 500 nanometers.Wavelengths longer than 500 nanometers may also be emitted by thesesources, although this is by no means necessary. It is preferred thatultraviolet light also be emitted, notwithstanding substantialabsorption by the hiding pigment because some ultraviolet light,particularly that in the near ultraviolet region of the spectrum, isavailable for photopolymerization purposes, particularly at or near thesurface of the coating remote from the substrate where absorption by thepigment has not yet reduced the number of ultraviolet light photons toinsubstantial values. The ultraviolet light, being more energetic thanactinic light of longer wavelengths, aids polymerization at or near thesurface of the coating. Examples of suitable sources are mercury arcs,carbon arcs, low pressure mercury lamps, medium pressure mercury lamps,high pressure mercury lamps, swirl-flow plasma arc, radio frequencyinduced mercury lamps and ultraviolet light emitting xenon flash lamps.Particularly preferred are ultraviolet light emitting lamps of themedium or high pressure mercury vapor type which also emit in thewavelength range of from about 380 to about 500 nanometers. Such lampsusually have fused quartz envelopes to withstand the heat and transmitthe ultraviolet and longer wavelength radiation and are ordinarily inthe form of long tubes having an electrode at either end. Examples ofthese lamps are PPG Models 60-2032, 60-0393, 60-0197 and 60-2031 andHanovia Models 6512A431, 6542A431, 6565A-431 and 6577A31.

The time of exposure to actinic light which has a wavelength such thatthe ultraviolet light absorbing hiding pigment is substantiallytransparent thereto and which is absorbable by the phenanthrenequinoneto produce free radicals capable of causing polymerization of acrylicgroups and the intensity of such actinic light to which the coatingcomposition is exposed may vary greatly. Generally, the exposure to theactinic light should continue until the C-stage is reached where thefilm is hard and infusible.

The thicknesses of polymerized coatings of the actinic lightpolymerizable composition of the invention are subject to widevariation. Usually, such thicknesses are in the range of from about0.001 millimeter to about 0.3 millimeter. More often, they are in therange of from about 0.005 millimeter to about 0.2 millimeter. Typically,they are in the range of from about 0.012 millimeter to about 0.15millimeter. When the actinic light polymerizable composition is anactinic light polymerizable printing ink, the polymerized coatingsusually have thicknesses in the range of from about 0.001 millimeter toabout 0.03 millimeter.

Substrates which may be coated with the compositions of this inventionmay vary widely in their properties. Organic substrates such as wood,fiberboard, particle board, composition board, paper, cardboard andvarious polymers such as polyesters, polyamides, cured phenolic resins,cured aminoplasts, acrylics, polyurethanes and rubber may be used.Inorganic substrates are exemplified by glass, quartz and ceramicmaterials. Many metallic substrates may be coated. Exemplary metallicsubstrates are iron, steel, stainless steel, copper, brass, bronze,aluminum, magnesium, titanium, nickel, chromium, zinc and alloys.

The photopolymerization of compounds containing sites of ethylenicunsaturation is often inhibited by the presence of oxygen. The oxygencontent of air is, in many instances, sufficient to preclude adequatepolymerization of the thin layer of the coating having a surface whichis adjacent to the air. In many cases, the interior of the coating maybe adequately polymerized producing what is known as adequate "throughcure", but oxygen inhibition causes the surface to remain tacky andunsuitable for most applications. This phenomenon is known in the art asinadequate "surface cure". Although it is not desired to be bound by anytheory, it is believed that the inhibition is due to the formation ofperoxide at the site of chain propagation which quenches the reactionand thereby terminates chain growth.

The photopolymerization of some compounds containing sites of ethylenicunsaturation is not significantly oxygen inhibited. Such materials maytherefore be polymerized in air. When oxygen inhibition is significant,or even when it is insignificant, the coatings may be polymerized invacuum or in an inert atmosphere, such as nitrogen, carbon dioxide,argon, methane, ethane, etc. where the oxygen concentration, if any, ismaintained below those concentrations causing significant oxygeninhibition. Oxygen may also be excluded by placing a film of removablematerial which is transparent to actinic light next to the resin,exposing the sandwiched coating to actinic light in air and thenstripping away the removable material. Another method to overcome theproblem of oxygen inhibition is to employ in the coating composition atleast one aromatic ketone or aromatic aldehyde photopolymerizationactivator which has a triplet energy in the range of from about 54kilocalories per mole to about 72 kilocalories per mole. Examples ofthese photopolymerization activators are benzil, benzophenone, methylphenyglycoxylate, ethyl phenylglyoxylate, butyl phenylglyoxylate andbutoxyethyl phenylglyoxylate. The esters of phenylglyoxylic acid may beprepared by reacting phenylglyoxyloyl chloride (Kharasch and Brown,Journal of the American Chemical Society, vol. 64, page 329 et seq.[1942]) with the appropriate alcohol. The amount of aromatic ketoneand/or aromatic aldehyde photopolymerization activator present in theactinic light polymerizable compositions of the invention may be widelyvaried. Usually, such photopolymerization activator is present in anamount in the range of from about 0.01 percent to about 50 percent basedon the weight of the binder of the coating composition. More often, anamount in the range of from about 0.1 percent to about 20 percent isemployed. From about 0.5 to about 10 percent by weight based on theweight of the binder is preferred.

The actinic light polymerizable coating compositions of the presentinvention are particularly useful for coating steel and aluminum foodand beverage cans.

In the illustrative examples which follow, all parts are parts by weightand percentages are percent by weight unless otherwise specified.

EXAMPLE I

A reactor equipped with a thermometer, a heater, a cooler, an agitator,a condenser set for a total reflux, a source of air and a source ofnitrogen is charged with 380.8 parts acrylic acid, 1.87 parts2,6-di-tertbutyl-4-methylphenol and 1.86 parts triphenyl phosphine andan air sparge is applied. The charge is then heated to 110° C. A mixturecomprising 385 parts epichlorohydrin and 166.6 parts Epon 828 bisphenolA-diglycidyl ether is preheated to about 110° C. Over a period of 4hours, 551.6 parts of the preheated mixture is added to the reactorwhile maintaining the temperature of the reaction mixture in the rangeof from 110° C. to 111.7° C. Upon completion of the addition, thetemperature of the reaction mixture is held in the range of from 110° C.to 113° C. for 75 minutes. At the end of this period (temperature:112.2° C.), heat is shut off and cooling is applied. Fifteen minuteslater (temperature: 96.1° C.), the condenser is set for distillation, aslight vacuum of 12 kilopascals (1 pascal=1 newton per square meter) isapplied while maintaining an air sparge, and distillation is begun. Twohours later (temperature: 97.8° C.), 21 parts distillate has beenremoved and the vacuum is removed. Thirty minutes later (temperature:97.2° C.), a slight vacuum of 10.7 kilopascals is applied whilemaintaining an air sparge and distillation is again begun. Two hourslater (temperature: 97.2°C.), 7 additional parts distillate has beenremoved and the vacuum and air sparge are removed. Fifteen minutes later(temperature: 97.8° C.), the vacuum and air sparge are reapplied. Thirtyminutes later (temperature: 97.8° C.), the vacuum and air sparge areremoved, heat is shut off and cooling is applied. Forty-five minuteslater when the temperature has reached 54.4° C., the product isdischarged through a filter into containers. This intermediate product,which is a mixture of 3-chloro-2-hydroxypropyl acrylate,2-chloro-1-(hydroxymethyl)ethyl acrylate and the diacrylate of Epon 828bisphenol A-diglycidyl ether, is found to have an acid number of 3.9, aGardner-Holdt viscosity of K, a hydroxyl number of 242 and to contain0.02 percent water and 14.1 percent chlorine.

A reactor equipped with an agitator, a heater, a packed distillationcolumn, a condenser, thermometers and a source of nitrogen is chargedwith 272.8 parts ethylene glycol, 296 parts phthalic anhydride and 0.57part butyl stannoic acid. A nitrogen sparge is applied, the contents ofthe reactor are heated to 195° C. and water is removed from the system.Fifty minutes later, the temperature has risen to 210° C. Thetemperature is then held in the range of from about 209° C. to about210° C. for 40 minutes while water is removed. At the end of this time,the distillation column is bypassed so that the vapor from the reactoris vented through a condenser in a manner such that condensate is notreturned to the reactor. The liquid is maintained at temperatures in therange of from about 209° C. to about 211° C. for 11/4 hours and thendischarged into containers. The product polyester resin has an acidnumber of 0.84, a Gardner-Holdt viscosity of Z-2⁺ and a total solidscontent greater than 99 percent.

A reactor equipped with a heater, a cooler, an agitator, a distillationcolumn, condenser, phase separator, a vacuum source, a source of air anda source of nitrogen is charged with 777 parts of the above polyesterresin, 475 parts acrylic acid, 173 parts toluene and 9.6 partshydroquinone. The condenser and phase separator are set for totalreflux. The reaction mixture is heated to 49° C. at an absolute pressureof about 80 kilopascals and 28.7 parts sulfuric acid is added. Theabsolute pressure is reduced to about 67 kilopascals and refluxing isobserved. The condenser and phase separator are set for azeotropicdistillation. One hour later, (temperature: 89° C; absolute pressure: 43kilopascals), 52 parts water has been removed. After another hour,(temperature: 94° C.; absolute pressure: 36 kilopascals), a total of 98parts water has been removed. After another 45 minutes, (temperature:85° C., absolute pressure: 24 kilopascals), a total of 102 parts waterhas been removed. Heat is then removed and cooling is applied. When thetemperature reaches 24° C., the vacuum is broken with nitrogen, 2210parts toluene and 170 parts normal hexane are added and the mixture iswell agitated. The mixture is then washed with 340 parts 20 percentaqueous sodium hydroxide solution using agitation while maintaining thetemperature below 27° C. Agitation is stopped and the phases are allowedto separate. The aqueous layer is removed and 25 parts sodium sulfate isadded and admixed with the organic phase. The mixture is filtered intocontainers to remove solid material. The filtrate (3188 parts) ischarged back into the reactor. A solution is prepared by admixing 1.6parts hydroquinone and 13.3 parts acetone and the solution (14.9 parts)is added to the reactor. The condenser is set for vacuum distillation. Avacuum is applied to reduce the absolute pressure to about 46.7kilopascals, the contents of the reactor are heated to 60° C. and theremoval of distillate is begun. The temperature of the liquid ismaintained in the range of from about 52° C. to about 60° C. for 8-1/3hours while the absolute pressure is gradually reduced to 13.3kilopascals and 1835 parts distillate is removed. During the next 3hours 25 minutes, the absolute pressure is inreased to 16 kilopascalsand the temperature is increased to 61° C. At this time, a total of 2263parts distillate has been removed. Distillation is stopped, heat isremoved and cooling is begun. When the temperature reaches 27° C., thevacuum is broken with nitrogen. The stripped product, amounting to 896parts, is admixed with 180 parts methanol and the mixture is subjectedto stripping by batch vacuum distillation until the temperature of theremaining liquid is 60° C. at an absolute pressure of 3.3 kilopascals.The product, amounting to 769 parts, is cooled to about 27° C., thevacuum is broken with nitrogen and the product is discharged intocontainers. This product, a polyester diacrylate composition, has asolids content of greater than 99 percent, an acid number of 0.84 and ahydroxyl number of 13.

A pigment paste is prepared by grinding 200 parts rutile (RTC 2, Tioxideof Canada) with 100 parts of the above polyester diacrylate composition.

A coating composition is prepared by admixing 300 parts of the abovepigment paste, 3 parts phenanthrenequinone, 300 parts of the aboveintermediate product and 6 parts benzophenone.

The coating composition is spread onto an aluminum substrate with anumber 024 wire wound bar to provide a film having a thickness of about0.03 millimeter. The coated substrate is passed once at 6.1 meters perminute, in air, under four medium pressure mercury vapor lamps, eachoperating at 78.7 watts per centimeter and emitting both ultravioletlight and visible light.

The lamps are 8.9 centimeters above the plane of the substrate surfaceand are spaced at intervals of about 20.3 centimeters. Passage of thecoated substrate under the lamps causes polymerization of the film andproduces a hard, adherent, white coating.

EXAMPLE II

A reactor equipped with a thermometer, a heater, a pressure equalizingdropping funnel, an agitator and an air sparge is charged with 725 partsacrylic acid, 4 parts 2,6-di-tert-butyl-p-cresol, 10 partsN,N-dimethylcyclohexylamine and 0.04 part hydroquinone. The charge isthen heated to 100° C. and 1300 parts neopentyl glycol diglycidyl ether(XD 7114, Dow Chemical Co.) is added dropwise over 3.67 hours. After theaddition is completed, the mixture is held at about 100° C. for 5.83hours and then cooled to produce a diacrylate of neopentyl glycoldiglycidyl ether product having an acid value of 14.

One hundred fifty parts of the above diacrylate of neopentyl glycoldiglycidyl ether and 300 parts RTC 2 rutile are ground using a Cowlesblade to form a fine intermediate paste. Three hundred parts of theabove diacrylate of neopentyl glycol diglycidyl ether is added to andadmixed with the intermediate paste to produce a pigment paste.

Coating Composition A is prepared by admixing 50 parts of the pigmentpaste and 1 part methyl phenylglyoxylate.

Coating Composition B is prepared by admixing 700 parts of the abovepigment paste and 7 parts of phenanthrenequinone using a Cowles bladeuntil the phenanthrenequinone dissolves.

Coating Composition C is prepared by admixing 50 parts of Composition Band 2 parts methyl phenylglyoxylate.

Coating Compositions D through H are each prepared by admixing 50 partsof Coating Composition B with 1 part of a photopolymerization activatoradditive, the identity of which is shown in Table 1.

Each coating composition is drawn down onto separate aluminum substrateswith a number 014 wire wound bar to provide films having thicknesses ofabout 0.02 millimeter. The coated substrates are each passed once at15.2 meters per minute, in air, under the four lamps of Example I. Theresults are shown in Table 1, which follows.

                                      Table 1                                     __________________________________________________________________________                                     Additive                                     Coating Phenanthrenequinone      Content                                                                             Through                                                                             Surface     60 %                 Composition                                                                           Content, Percent                                                                          Additive     Percent                                                                             Cure  Cure  Color Gloss                __________________________________________________________________________    A       0           methyl phenylglyoxylate                                                                    1.96  poor  mar free                                                                            white 83                   B       0.99        none         0     excellent                                                                           easily                                                                              yellow                                                                              76                                                                scratched                        C       0.95        methyl phenylglyoxylate                                                                    3.85  excellent                                                                           mar free                                                                            white 83                   D       0.97        methyl phenylglyoxylate                                                                    1.96  excellent                                                                           mar free                                                                            white 81                   E       0.97        benzophenone 1.96  excellent                                                                           mar free                                                                            86                         F       0.97        benzil       1.96  excellent                                                                           mar free                                                                            slightly                                                                            83                                                                      yellow                     G       0.97        2-methylanthraquinone                                                                      1.96  excellent                                                                           mar free                                                                            slightly                                                                            82                                                                      yellow                     H       0.97        2-chlorothioxanthone                                                                       1.96  excellent                                                                           mar free                                                                            slightly                                                                            81                                                                      yellow                     __________________________________________________________________________

EXAMPLE III

One hundred parts of the diacrylate of neopentyl glycol diglycidyl etheris admixed with 200 parts titanium dioxide (R960; E. I. duPont deNemours and Co.) and ground to a fine paste with a Cowles blade. Threeparts phenanthrenequinone is then added and ground into the paste with aCowles blade. To the resulting mixture are added 300 parts of thediacrylate of neopentyl glycol diglycidyl ether, 20 parts methyl ethylketone and 9 parts ethyl phenylglyoxylate. The whole is admixed to forman intermediate composition.

To 90 parts of the above intermediate composition are added 10 parts ofmethyl ethyl ketone and 10 parts of a 5 percent dispersion of phthaloblue pigment in the diacrylate of neopentyl glycol diglycidyl ether.After mixing, the resulting composition is filtered to produce asprayable coating composition.

The sprayable coating composition is sprayed onto a metal substrate toform a film having a thickness of about 0.05 millimeter. The coatedsubstrate is passed once at 3.05 meters per minute, in air, under thefour lamps of Example I to polymerize the film into a hard, adherent,blue coating having a high gloss.

EXAMPLE IV

A reactor equipped with a thermometer, a heater, an addition funnel andan agitator is charged with 918 parts propylene carbonate. The charge isthen heated to about 60° C. Over a period of one hour, 675 partsN-methylethanolamine is added while maintaining the temperature of themixture at 60 to 70° C. Upon completion of the addition, the mixture isheld at 60° to 70° C. for one hour and cooled to produce a first polyolintermediate.

A loop reactor equipped with a steam heated heater on one leg, a cooleron the other leg, a thermometer, a pressure gauge and a pump forcirculating liquid in the loop is charged with 1210 parts of the firstpolyol intermediate and 14 parts crushed sodium hydroxide. The charge isheated to 99° C. and maintained in a range of from 99° C. to 108° C. ata pressure in the range from about 206 to about 290 kilopascals gaugefor about 4-1/2 hours during which time 970 parts propylene oxide isadded. The reactor is cooled and vented and 14 parts crushed sodiumhydroxide is added. The reaction mixture is heated to 99° C. andmaintained in the range of from 99° C. to 107° C. at a pressure of fromabout 138 to about 311 kilopascals gauge for about 1-3/4 hours duringwhich time 350 parts propylene oxide is added. The reactor is cooled.The next morning, the reactor is heated to 102° C. and maintained in therange of from 101° C. to 107° C. at a pressure of from about 206 toabout 345 kilopascals gauge for about one hour during which time 270parts propylene oxide is added. The reactor is held at a temperature offrom 105° C. to 110° C. at a pressure of from about 311 to about 345kilopascals gauge for about 3/4 hour. The reactor is then cooled andvented, and the liquid contents of the reactor are drained into acontainer. The container is found to contain 2688 parts of product whichis a second polyol intermediate.

To 2688 parts of the second polyol intermediate is added 28 parts of 86percent phosphoric acid at 60° C. After mixing, a sample of the reactionmixture is taken and diluted with an equal weight of water. The pH ofthe diluted sample is measured and found to be less han 7.0. A vacuum isapplied to the reaction mixture and the reaction mixture is heated to120° C. and held at that temperature for one-half hour. The vacuum isthen released, and one percent diatomaceous earth filter aid (Hy-Flo),based on the weight of total charge, is added. The mixture is thenfiltered in a pressure filter to form a third polyol intermediate.

A reactor equipped with a therometer, a heater, an addition funnel, anagitator and an air sparge is charged with 222 parts1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, 132 partsphenylcellulose acrylate, 1 part N,N-dimethylcyclohexylamine and 0.2part dibutyl tin dilaurate. The charge is heated to 50° C. Over a periodof one hour, 178 parts of the third polyol intermediate is added. Uponcompletion of the addition, the reaction mixture is held at 50° C. forone hour and then at 70° C. for two hours. Over a period of 5 to 10minutes at 70° C. under an air sparge, 0.5 part2,6-di-tert-butyl-p-cresol and 130 parts 2-hydroxyethyl acrylate areadded. The reaction mixture is held at 70° C. for six hours. Twenty-fiveparts 2-hydroxyethyl acrylate is added. The reaction mixture is thenheld at 85° C. for two hours and cooled to produce a polyurethaneterminated with acrylyl groups.

A reactor equipped with a thermometer, a heater, a pressure equalizingaddition funnel and an agitator is charged with 275 parts acrylic acid,4 parts N,N-dimethylcyclohexylamine, 1.6 parts2,6-di-tert-butyl-p-cresol and 0.015 part hydroquinone. The charge isthen heated to 100° C. and 500 parts 1,4-butanediol diglycidyl ether(Araldite RD-2, Ciba Geigy) is added dropwise over 6 hours. After theaddition is completed, the mixture is held at 100° C. for 2 hours andthen cooled to produce a diacrylate of 1,4-butanediol diglycidyl etherproduct having an acid value of 6.

One hundred parts of the diacrylate of 1,4-butanediol diglycidyl etherand 150 parts titanium dioxide are combined and ground to a fine paste.

A coating composition is prepared by admixing 25 parts of the above finepaste, 5 parts 2-hydroxyethyl acrylate, 15 parts of the polyurethaneterminated with acrylyl groups, 0.45 part phenanthrenequinone and 0.45part ethyl phenylglyoxylate.

The coating composition is drawn down on an aluminum substrate with anumber 009 wire wound bar to provide a film having a thickness of about0.01 millimeter. The coated substrate is passed once at 45.7 meters perminute, in air, under the four lamps of Example I to produce a tough,nearly completely adherent coating.

The coating composition is drawn down on an aluminum substrate with anumber 026 wire wound draw bar to provide a film having a thickness ofabout 0.03 millimeter. The coated substrate is exposed to the four lampsof Example I to produce a flexible coating having high gloss.

EXAMPLE V

One hundred parts of the intermediate product of Example I, viz., themixture of 3-chloro-2-hydroxypropyl acrylate,2-chloro-1-(hydroxymethyl)-ethyl acrylate and the diacrylate of Epon 828bisphenol A-diglycidyl ether, and 100 parts RTC 2 rutile are ground to afine paste. A coating composition is prepared by adding to the paste 100additional parts of the intermediate product of Example I and 3 partsphenanthrenequione and again grinding to a fine paste.

The coating composition is drawn down onto an aluminum substrate with anumber 006 wire wound bar to provide a film having a thickness of about7.6 micrometer. The coated substrate is passed once, at 12.2 meters perminute, in a nitrogen atmosphere containing about 200 parts oxygen permillion parts atmosphere by volume, under the four lamps of Example I toproduce a hard, infusible coating having a 60° gloss of 87.

I claim:
 1. An actinic light polymerizable coating compositionconsisting essentially of:a. phenanthrenequinone, saidphenanthrenequinone being present in an amount in the range of fromabout 0.01 percent to about 10 percent by weight based on the weight ofthe binder of said coating composition; b. organic polymerizablematerial containing a plurality of sites of ethylenic unsaturation andcapable of being free radically addition polymerized by interaction withsaid phenanthrenaquinone upon exposure to actinic light, said organicpolymerizable material comprising polymer having a plurality of sites ofacrylic unsaturation, monomer having a plurality of sites of acrylicunsaturation or mixture thereof, said organic polymerizable materialbeing present in an amount in the range of from about 20 percent toabout 100 percent by weight of the binder of said coating composition;and c. rutile, said rutile being present in an amount in the range offrom about 5 percent to about 70 percent by weight of said coatingcomposition.
 2. A method comprising:a. coating a substrate with anactinic light polymerizable coating composition consisting essentiallyof:1. phenanthrenequinone, said phenanthrenequinone being present in anamount in the range of from about 0.01 percent to about 10 percent byweight based on the weight of the binder of said coating composition, 2.organic polymerizable material containing a plurality of sites ofethylenic unsaturation and capable of being free radically additionpolymerized by interaction with said phenanthrenequinone upon exposureto actinic light, said organic polymerizable material comprising polymerhaving a plurality of sites of acrylic unsaturation, monomer having aplurality of sites of acrylic unsaturation or mixture thereof, saidorganic polymerizable material being present in an amount in the rangeof from about 20 percent to about 100 percent by weight of the binder ofsaid coating composition, and
 3. rutile, said rutile being present in anamount in the range of from about 5 percent to about 70 percent byweight of said coating composition: b. exposing said coated substrate toactinic light having a wavelength in the range of from about 380 toabout 500 nanometers to thereby polymerize said coating into a hard,infusible film.
 3. The method of claim 2 wherein during said exposure,said coating is also simultaneously exposed to ultraviolet light.